Article
Polymer Science
Alejandra Romero-Montero, Isabel S. Aguirre-Diaz, Jordi Puiggali, Luis J. del Valle, Miquel Gimeno
Summary: The self-assembly behavior and nano-morphologies of chemoenzymatic high molecular weight poly-l-phenylalanine (ePLP) were investigated. The addition of HFIP co-solvent induced a transition from a non-ordered secondary structure to an alpha-helix, with temperature and hydrogen bonding playing important roles in structural stabilization and nanotube formation. The highly homogeneous nanotubes showed stable conductivity and high orientation and stabilization by intra- and intermolecular hydrogen bonds, allowing for potential drug delivery applications.
Article
Polymer Science
Zhengyu Piao, Jin Kyung Park, Madhumita Patel, Hyun Jung Lee, Byeongmoon Jeong
Summary: This study found that poly(L-alanine-co-L-lysine) (PAK) exhibits IRI activity similar to poly(vinyl alcohol) and generates cubic-to-spherical shaped ice crystals, showing superior performance. In contrast, poly(L-alanine-co-L-aspartic acid) (PAD) and poly(ethylene glycol) (PEG) with similar molecular weights did not provide significant IRI activity. FTIR and circular dichroism spectroscopies indicated that PAK forms alpha-helices, while PAD forms random coils in water. Additionally, dynamic ice shaping study suggested strong interaction between PAK and ice crystals, while PAD and PEG only weakly interact.
Article
Chemistry, Organic
Beata Zdun, Tamara Reiter, Wolfgang Kroutil, Pawel Borowiecki
Summary: We developed chemoenzymatic routes using low-cost starting materials and enzyme preparations to synthesize tenofovir. The key step involved stereoselective reduction or kinetic resolution using alcohol dehydrogenase or lipase as biocatalysts. By employing immobilized lipase in a mixture of vinyl acetate and toluene, the desired (R)-ester was obtained with high yield and optical purity. Alternatively, reduction of a ketone using lyophilized E. coli cells containing recombinant alcohol dehydrogenase resulted in excellent conversion and yield of the corresponding (R)-alcohol. The enzymatic strategy could be applied in the synthesis of tenofovir prodrug derivatives.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Alexander Rittner, Mirko Joppe, Jennifer J. Schmidt, Lara Maria Mayer, Simon Reiners, Elia Heid, Dietmar Herzberg, David H. Sherman, Martin Grininger
Summary: This study reports a strategy to introduce fluorine into complex polyketides during biosynthesis. By exchanging a domain of the polyketide synthase, the ability to incorporate fluorine during polyketide chain extension was achieved. The results demonstrate the potential application of this method in the chemoenzymatic synthesis of fluorinated compounds.
Article
Chemistry, Organic
Evan O. Romero, Jonathan C. Perkins, Jessica E. Burch, David A. Delgadillo, Hosea M. Nelson, Alison R. H. Narayan
Summary: The first asymmetric synthesis of the pentacyclic fungal marine natural product Xyloketal B is described using a chemoenzymatic strategy. The approach utilizes a biocatalytic benzylic hydroxylation and a [4 + 2] cycloaddition to access key intermediates enroute to (+)-xyloketal B. MicroED is used to confirm the relative configuration of an intermediate, and a reductive approach is employed to access a second key intermediate, culminating in the stereoselective synthesis of (+)-xyloketal B.
Review
Chemistry, Multidisciplinary
Suman Chakrabarty, Evan O. Romero, Joshua B. Pyser, Jessica A. Yazarians, Alison R. H. Narayan
Summary: The total synthesis of structurally complex natural products remains an exciting area of research, with recent advancements in biocatalysis allowing for the application of enzymes in constructing complex molecules. The utilization of enzymes alongside small molecule-based approaches has enabled concise chemoenzymatic routes to natural products, demonstrating the potential for selective oxidation reactions and late-stage diversification of complex scaffolds.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Materials Science, Multidisciplinary
Yanyan Li, Junhe Chen, Wanli Han, Hongling Yi, Jianning Wang, Peixiang Xing, Jiaxiang Ren, Donggang Yao
Summary: The addition of calcium oxide (CaO) to PET enables its degradation in water, as demonstrated in this study. PET/CaO composite samples are prepared and tested for hydrolysis in water, showing thermal stability during processing and controlled degradation to form calcium terephthalate. The mechanically strong PET/CaO composite can be further promoted for hydrolysis by additional fillers, potentially impacting applications in disposable packaging and water dissolvable composite products.
MACROMOLECULAR MATERIALS AND ENGINEERING
(2022)
Article
Plant Sciences
Manuel G. Schriefer, Rainer Schobert
Summary: In this study, the six recently isolated berkeleylactones E, J, K, M, N, and O were successfully synthesized for the first time using a divergent strategy from a common intermediate in the synthesis of berkeleylactone A. Key achievements include the stereoselective formation of the gamma,delta-dihydroxy-alpha,beta-unsaturated ester moiety and the development of a general protection group strategy. Additionally, a short and high-yielding formal synthesis of the commonly synthesized antibiotic A26771B was established.
JOURNAL OF NATURAL PRODUCTS
(2023)
Article
Nanoscience & Nanotechnology
Yiwen Xi, Prashant Kumar Sharma, Hans Jan Kaper, Chang-Hwan Choi
Summary: The study investigated the tribological properties of micropored pHEMA under physiologically relevant conditions, finding that it significantly reduced frictional energy dissipation at relatively high loads and sliding speeds. This was attributed to the greater amount and retentivity of the interfacial fluid supported by the free water squeezed out of micropores with smaller dimensions under higher load and sliding speed.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Organic
Jordan T. Brazeau-Henrie, Andre R. Paquette, Allison Q. . O'Rourke, Michael G. Darnowski, Christopher N. Boddy
Summary: The total and chemoenzymatic synthesis of the depsipeptide natural product seongsanamide E, 3, is described. The synthetic C-terminal N-acetylcysteamine thioester of linear natural product 1 was macrolactonized by the excised recombinant purified seongsanamide thioesterase (Sgd-TE) domain, generating 3. Sgd-TE also effects the ring opening of 3. Chemical synthesis provided 3 through a macrolactamization strategy. This work confirms the biosynthesis of 3 and demonstrates the power of Sgd-TE as a biocatalyst.
Article
Polymer Science
Isaac Benavides, Timothy J. Deming
Summary: We have prepared a new water-soluble, nonionic homopolypeptide poly(L-homoserine) and poly(L-homoserine) block copolymers with controllable segment lengths. The conformational preferences of poly(L-homoserine) in both the solid state and in solution have been determined. Poly(L-homoserine) is soluble in water and adopts a disordered conformation, making it a promising candidate for applications in biology as a nonionic, water-soluble homopolypeptide. Towards this goal, a poly(L-homoserine) containing a block copolypeptide has been prepared and found to self-assemble into micro- and nanoscale vesicles in water.
Article
Polymer Science
Isaac Benavides, Timothy J. Deming
Summary: We have successfully prepared a new water-soluble, nonionic homopolypeptide poly(L-homoserine), as well as poly(L- homoserine) block copolymers with controllable segment lengths. The conformational preferences of poly(L-homoserine) were determined in both the solid state and in solution. The poly(L-homoserine) showed promising potential for applications in biology due to its solubility in water and disordered conformation. To further explore its potential, a block copolypeptide containing poly(L-homoserine) was prepared and found to self-assemble into micro- and nanoscale vesicles in water.
Article
Agricultural Engineering
Changqing Wu, Cuiluan Ma, Qing Li, Haoyu Chai, Yu-Cai He
Summary: In this study, efficient and sustainable conversion of waste bread to 5-hydroxymethyl-2-furoamine was achieved through a cascade reaction using betaine:malonic acid-water. The waste bread was synthesized into 5-HMF in 45 minutes at 190℃, with a yield of 30.3 wt%. By using recombinant E. coli cells, the 5-HMF was then biologically aminated into HMFA with a high yield of 92.1% at 35℃ for 12 hours. This two-step chemical-enzymatic cascade reaction provides a new strategy for the synthesis of valuable furan chemicals from waste biomass.
BIORESOURCE TECHNOLOGY
(2023)
Article
Biochemistry & Molecular Biology
Wei He, Jiacheng Ni, Yu-Cai He, Jianren Ye
Summary: Efficient synthesis of furan-based chemicals from biomacromolecule using chemoenzymatic approaches has been developed in this study. Different biomass sources can produce varying concentrations of furfural, and the conversion of furfural to furfurylamine is inhibited by by-products and soluble sugars produced during the biomass conversion. The amination of furfural to furfurylamine can be achieved by using specific enzymes. This study successfully developed a chemoenzymatic strategy for the conversion of biomacromolecules into valuable furan-based products in an environmentally friendly system.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2022)
Article
Multidisciplinary Sciences
Tao Cai, Hongbing Sun, Jing Qiao, Leilei Zhu, Fan Zhang, Jie Zhang, Zijing Tang, Xinlei Wei, Jiangang Yang, Qianqian Yuan, Wangyin Wang, Xue Yang, Huanyu Chu, Qian Wang, Chun You, Hongwu Ma, Yuanxia Sun, Yin Li, Can Li, Huifeng Jiang, Qinhong Wang, Yanhe Ma
Summary: Researchers have developed an artificial starch anabolic pathway (ASAP) in a cell-free system for starch synthesis from CO2 and hydrogen, achieving a significantly higher rate than traditional methods. This approach paves the way for future chemo-biohybrid starch synthesis from CO2.
Article
Biochemical Research Methods
Choon Pin Foong, Mieko Higuchi-Takeuchi, Kenji Ohtawa, Takuya Asai, Hanqin Liu, Yasuyuki Ozeki, Keiji Numata
Summary: Polyhydroxyalkanoates (PHAs) are sustainable bioplastics that can replace synthetic plastics without causing environmental threats. Using marine photosynthetic purple nonsulfur bacteria (PNSBs), sustainable PHA production can be achieved. However, the economic feasibility of PHA production using PNSBs has been limited due to high cost and low productivity. In this study, researchers improved PHA productivity by creating enhanced mutants of Rhodovulum sulfidophilum, which reached the stationary growth phase and accumulated maximum PHA content faster than the wild type.
ACS SYNTHETIC BIOLOGY
(2022)
Article
Materials Science, Biomaterials
Naoto Yoshinaga, Keiji Numata
Summary: Mitochondria play a crucial role in cellular metabolism and mutations in mitochondrial DNA can lead to inherited diseases. Gene delivery systems targeting mitochondria have been developed to address mitochondrial DNA mutations, but further exploration and optimization are needed for effective mitochondrial gene therapy.
ACS BIOMATERIALS SCIENCE & ENGINEERING
(2022)
Article
Biochemistry & Molecular Biology
Yan Zhao, Zihong Wu, Lei Chen, Xiong Shu, Juan Guan, Kang Yang, Ruya Shi, Yibin Li, Keiji Numata, Zhengzhong Shao
Summary: Natural fiber-reinforced biocomposites with excellent mechanical and biological properties have attractive prospects for internal medical devices. However, poor interfacial adhesion between natural silk fiber and the polymer matrix has been a disturbing issue for such applications. In this study, rigid-flexible agents, such as polydopamine (PDA) and epoxy soybean oil (ESO), were introduced to enhance the interfacial adhesion between Antheraea pernyi (Ap) silk and polycaprolactone (PCL). The Ap-PDA-ESO strategy exhibited a greater enhancement in interfacial adhesion, and proposed interfacial toughening mechanisms.
Article
Plant Sciences
Kazuya Ishikawa, Makoto Kobayashi, Miyako Kusano, Keiji Numata, Yutaka Kodama
Summary: By using the organelle glue technique, we manipulated organelle interactions and controlled the plant metabolome at the pathway level. This study demonstrates the potential for designing plants with desirable metabolic activities by artificially controlling organelle interactions through genetic modification.
PLANT CELL REPORTS
(2023)
Article
Multidisciplinary Sciences
Kazusato Oikawa, Shino Goto-Yamada, Yasuko Hayashi, Daisuke Takahashi, Yoshitaka Kimori, Michitaro Shibata, Kohki Yoshimoto, Atsushi Takemiya, Maki Kondo, Kazumi Hikino, Akira Kato, Keisuke Shimoda, Haruko Ueda, Matsuo Uemura, Keiji Numata, Yoshinori Ohsumi, Ikuko Hara-Nishimura, Shoji Mano, Kenji Yamada, Mikio Nishimura
Summary: Pexophagy plays a pivotal role in selectively removing ROS-generating peroxisomes under high-intensity light, which protects plants from oxidative damage during photosynthesis.
NATURE COMMUNICATIONS
(2022)
Article
Biochemistry & Molecular Biology
Nur Alia Oktaviani, Ali D. Malay, Akimasa Matsugami, Fumiaki Hayashi, Keiji Numata
Summary: Spider dragline silk, composed of spidroins MaSp1 and MaSp2, is an incredibly tough biomaterial. The N-terminal domains (NTDs) of spidroins undergo rapid dimerization in response to a pH gradient during fiber self-assembly. In this study, the solution structures of MaSp1 and MaSp2 NTDs from Trichonephila clavipes were determined, and the experimental pKa values of conserved residues involved in dimerization were measured using NMR. The unusual pKa values of specific residues, such as Asp40, Glu119, and Glu79, contribute to the tight spatiotemporal control of spider silk self-assembly.
Article
Biochemistry & Molecular Biology
Naoto Yoshinaga, Ayaka Tateishi, Yasuaki Kobayashi, Tomohiro Kubo, Hitoshi Miyakawa, Kotaro Satoh, Keiji Numata
Summary: Biodegradable polymers are eco-friendly materials that do not accumulate in the environment, making them attractive for use in a sustainable society. However, the chemical toxicities of their degradation products have not been well assessed. This study evaluated the toxic effects of biodegradable polyester, polycaprolactone (PCL), and synthetic oligocaprolactones (OCLs) with different polymerization degrees. The results showed that while PCL did not have adverse effects on organisms, high concentrations of shorter OCLs and the monomer had toxic effects on freshwater microorganisms, marine algae, and mammalian cells. This highlights the importance of understanding the effects of degradation products for ensuring a genuinely sustainable society.
Article
Biochemistry & Molecular Biology
Hiroyuki Nakamura, Nobuaki Kono, Masaru Mori, Hiroyasu Masunaga, Keiji Numata, Kazuharu Arakawa
Summary: This study compares the mechanical properties and water resistance of spider's minor ampullate silk (MI-silk) and major ampullate silk (MA-silk), revealing the unique properties and water resistance of MI-silk. Proteomic analysis shows that MI-silk is composed of minor ampullate spidroin (MiSp), major ampullate spidroin (MaSp1), and spidroin constituting elements (SpiCEs). The absence of MaSp2 in the MI-silk proteome explains the difference in water resistance between MI-silk and MA-silk.
Review
Biochemistry & Molecular Biology
Risa Naka, Kousuke Tsuchiya, Keiji Numata
Summary: Zwitterionic molecules, such as ZILs and ZIPs, can loosen cell wall networks and enhance the penetration of nanocarriers, increasing their transfection efficiency in targeted subcellular organelles in plants.
Article
Polymer Science
Kousuke Tsuchiya, Joan Gimenez-Dejoz, Keiji Numata
Summary: This study investigated the process of cationic peptides condensing plasmid DNA through atomic MD simulations. It was found that the peptides bind to the DNA and induce defects, leading to the folding of the DNA into a globule morphology. These findings provide insight into the mechanism of peptide-mediated gene delivery systems.
Article
Multidisciplinary Sciences
Kazuya Ishikawa, Xiaonan Xie, Yasuhide Osaki, Atsushi Miyawaki, Keiji Numata, Yutaka Kodama
Summary: Plants are able to produce bilirubin in chloroplasts through a nonenzymatic reaction, which helps maintain the redox status in chloroplasts.
Article
Chemistry, Multidisciplinary
Simon Sau Yin Law, Masato Asanuma, Jingwen Shou, Yasuyuki Ozeki, Yutaka Kodama, Keiji Numata
Summary: Plants can respond to various stresses by activating multiple signaling and defense pathways. The use of bioorthogonal probes allows for real-time visualization and quantification of these pathways, which has practical applications in characterizing plant responses to stress.
Article
Biochemistry & Molecular Biology
Naoya Abe, Seiya Fujita, Takaaki Miyamoto, Kousuke Tsuchiya, Keiji Numata
Summary: Plant mitochondria are crucial for metabolism and respiration. Mitochondrial transformation has gained interest for developing crops with valuable traits. In this study, a peptide-based carrier called Cytcox/KAibA-Mic was developed for efficient transfection into plant mitochondria. The modification rates of mitochondrial targeting and cell membrane-penetrating peptides were quantified and controlled. The gene carrier size remained constant despite changes in the mitochondrial targeting peptide modification rate. This gene carrier allows for quantitative investigation of peptide modifications and optimization of conditions for mitochondrial transfection.
Article
Materials Science, Biomaterials
Chonprakun Thagun, Tomohiro Suzuki, Yutaka Kodama, Keiji Numata
Summary: A plant cell-based expression platform was developed to produce complete MaSp2 protein, which self-assembles into spider silk nanofibrils. Overexpression of recombinant secretory MaSp2 proteins in transgenic BY-2 cell lines yielded 0.6-1.3 μg L-1 at 22 days, four times higher than cytosolic expressions. Expression of functional domain-truncated MaSp2 proteins lacking the C-terminal domain increased recombinant protein secretion from 0.9 to 2.8 mg L-1 per day within 7 days. These findings demonstrate significant improvement in extracellular production of spider silk spidroins using plant cells and reveal the regulatory roles of the MaSp2 C-terminal domain.
Review
Chemistry, Multidisciplinary
Simon Sau Yin Law, Takaaki Miyamoto, Keiji Numata
Summary: Genetic engineering has revolutionized agriculture and the use of nanomaterials has further enhanced the benefits. Subcellular targeting using nanomaterials has become possible but remains challenging despite its promise in organellar engineering.
CHEMICAL COMMUNICATIONS
(2023)
